Reactive disazo dyes containing halopyrimidyl and sulfonyl groups

ABSTRACT

Reactive dyes of the formula ##STR1## in which D is the radical of a dye of the polyazo or metal complex azo series, R 1  is hydrogen or an unsubstituted or substituted C 1-4  -alkyl radical, and X is the vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-chloroethyl or β-acetoxyethyl group, are suitable in particular for dyeing and printing cellulose-containing fibre materials by the cold pad-batch method and produce, in high dyeing yields, dyeings and prints having good fastness properties.

The present invention relates to novel reactive dyes, to a process fortheir preparation, and to their use for dyeings and printing fibrematerials.

The practice of dyeing with reactive dyes has in recent years led toincreased demands on the quality of the dyeing and the economics of thedyeing process. There consequently continues to be a demand for newreactive dyes with improved properties, in particular applicationproperties.

The demand these days in the dyeing of cotton by the cold pad-batchmethod is for reactive dyes which are sufficiently substantive at thelow dyeing temperature and which also have good wash-off properties whenunfixed. They should also be highly reactive, so that only shortbatching times are required, and they should in particular producedyeings having high degrees of fixation. Existing dyes meet theserequirements only to an insufficient degree.

It is therefore the object of the present invention to provide new,improved reactive dyes for the cold padbatch method which have thequalities characterised above to a high degree. The new dyes should bedistinguished especially by high degrees of fixation and high fibre-dyebond stabilities, and the unfixed portions on the fibre should moreoverbe readily washed off. They should also produce dyeings having goodall-round fastness properties, for example light- and wet-fastnessproperties.

This object is achieved with the novel bireactive dyes definedhereinafter.

The invention provides reactive dyes of the formula ##STR2## in which Dis the radical of a dye of the polyazo or metal complex azo series, R₁is hydrogen or an unsubstituted or substituted C₁₋₄ -alkyl radical, andX is a vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-chloroethyl orβ-acetoxyethyl group.

The radical D in the formula (1) can be substituted in the customarymanner. Examples of further substituents on the radical D are alkylgroups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl,isopropyl or butyl, alkoxy groups having 1 to 4 carbon atoms, such asmethoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups having1 to 8 carbon atoms, such as acetylamino, propionylamino orbenzoylamino, amino, alkylamino having 1 to 4 carbon atoms, such asmethylamino, ethylamino, propylamino, isopropylamino or butylamino,phenylamino, N,N-di-β-hydroxyethylamino, N,N-di-β-sulfatoethylamino,sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4carbon atoms in the alkoxy radical, such as methoxycarbonyl orethoxycarbonyl, alkylsulfonyl having 1 to 4 carbon atoms, such asmethylsulfonyl or ethylsulfonyl, trifluoromethyl, nitro, cyano, halogen,such as fluorine, chlorine or bromine, carbamoyl, N-alkylcarbamoylhaving 1 to 4 carbon atoms in the alkyl radical, such asN-methylcarbamoyl or N-ethylcarbamoyl, sulfamoyl, N-alkylsulfamoylhaving 1 to 4 carbon atoms, such as N-methylsulfamoyl,N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl,N-(β-hydroxyethyl)-sulfamoyl, N,N-di-(β -hydroxyethyl)-sulfamoyl,N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo.The radical D preferably contains one or more sulfonic acid groups.Reactive dyes of the formula (1) contain as substituents especiallymethyl, ethyl, methoxy, ethoxy, acetylamino, benzoylamino, amino,chlorine, bromine, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo.

An alkyl radical R₁ is straight-chain or branched; it can be furthersubstituted, for example by halogen, hydroxyl, cyano, C₁₋₄ -alkoxy,carboxyl or sulfo. Examples of R₁ and R₂ are the radicals methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl,carboxymethyl, β-carboxyethyl, β-carboxypropyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, β-methoxyethyl, β-ethoxyethyl, β-methoxypropyl,β-chloroethyl, γ-bromopropyl, β-hydroxyethyl, β-hydroxyethyl,β-hydroxybutyl, sulfomethyl, β-sulfoethyl, aminosulfonylmethyl andβ-sulfatoethyl. R₁ is preferably hydrogen, methyl or ethyl.

Preferred reactive dyes have the formula (1) in which D is the radicalof a disazo dye or of a corresponding metal complex azo dye. In thiscase the reactive radicals, i.e. the vinyl or β-sulfatoethyl etc.-sulfonyl radical and the 2,4-difluoro-5-chloropyrimidyl radical arebonded to different or identical radicals of starting components, namelydiazo and coupling components. The reactive dyes then for example havethe formula ##STR3## in which R₁ and X are as defined under the formula(1), D₁ and D₂ each are the radical of a diazo component, and K is theradical of a coupling component. If two X--SO₂ reactive radicals arepresent, they are bonded in particular to the radical of the diazocomponent; and in the case where the dye molecule contains two2,4-difluoro-5-chloropyrimidyl radicals, these are preferably in thecoupling component. Accordingly, depending on the indices attached tothe reactive radicals in the formula (1), trireactive and tetrareactivedyes are also included. The above explanations also hold analogously formetal complex azo dyes.

Also included are reactive dyes of the formula (1) in which one of thereactive radicals or both are bonded to the chromophore via a radical ofthe formula ##STR4## the X--SO₂ -- radical or the2,4-difluoro-5-chloropyrimidylamino radical being bonded to E; E is anunsubstituted or substituted aliphatic or aromatic bridge member. Thebridge member E is preferably an alkylene or arylene radical. Forinstance, E can be a long (for example of 10 or more carbon atoms) orshorter, straight-chain or branched alkylene radical; it can be inparticular an alkylene radical having 2 to 6 carbon atoms, for exampleethylene, propylene, butylene, hexylene or cyclohexylene. An aryleneradical E is for example a naphthylene radical, the radical of adiphenyl or of stilbene or in particular a phenylene radical. Theradical E can contain further substituents, for example halogen atoms,such as fluorine, chlorine and bromine, alkyl groups having 1 to 4carbon atoms, such as methyl, ethyl and propyl, alkoxy groups having 1to 4 carbon atoms, such as methoxy, ethoxy, propyloxy and isopropyloxy,carboxyl or sulfo. R and R', independently of each other, are eachhydrogen or an unsubstituted or substituted C₁₋₄ -alkyl radical; and Yis a halogen atom, a substituted or unsubstituted amino group, hydroxyl,or an alkoxy, aryloxy, alkylthio or arylthio group.

Preference is given to reactive dyes of the formula ##STR5## in which Xis as defined under the formula (1), and the benzene and naphthalenerings A, B and B', independently of one another, can be furthersubstituted; reactive dyes of the formula ##STR6## in which X is asdefined under the formula (1), and the benzene rings A and B,independently of each other, can be further substituted.

Preference is also given to reactive dyes of the formulae (2) and (3) inwhich the benzene rings A and B or B' are not further substituted and/orin which X is the vinyl or β-sulfatoethyl group.

The process for preparing the reactive dyes of the formula (1) comprisesreacting dyes of the formula ##STR7## in which D, R₁ and X are asdefined under the formula (1), or their precursors, with2,4,6-trifluoro-5-chloropyrimidine to reactive dyes of the formula (1),or converting the resulting intermediates into the desired end dyes, andif desired subsequently carrying out a further conversion reaction.

The starting materials are thus dyes which already contain an X--SO₂ --group, and the --N(R₁)H group is acylated with2,4,6-trifluoro-5-chloropyrimidine; or use is made of correspondingprecursors, for example a diazo component of the formula ##STR8## andthese precursors are coupled onto a coupling component which contains an--N(R₁)H group and the --N(R₁)H group is acylated before or after thecoupling with 2,4,6-trifluoro-5-chloropyrimidine. In the embodimentdescribed above, the acylatable --N(R₁)H group can also be present inthe diazo component, and the X--SO₂ -- group correspondingly in thecoupling component. The diazo components used in this case areespecially 1,3-phenylenediamine-4-sulfonic acid,1,4-phenylenediamine-2-sulfonic acid,1,4-phenylenediamine-2,5-disulfonic acid or1,3-phenylenediamine-4,6-disulfonic acid. If desired use is made ofcorresponding acetylamino and nitro compounds in which the acetylaminoand nitro groups respectively are converted into the H2N group byhydrolysis and reduction respectively before the condensation with2,4,6-trifluoro-5-chloropyrimidine. The position of the reactiveradicals in the finished azo dye is thus not inflexibly tied to certainstarting components - diazo or coupling components. The X--SO₂ radicaland the 2,4-difluoro-5-chloropyrimidyl radical can, for example in thecase of disazo dyes of the type

    D.sub.1 →M←D.sub.2,

also be bonded for one diazo component in each case.

The two reactive radicals can also be bonded to one and the samecomponent, for example by using a non-fibre-reactive diazo component anda coupling component of the formula ##STR9## and acylating the --NH₂group after the coupling with 2,4,6-trifluoro-5-chloropyrimidine.

Another advantageous method comprises first of all preparing a dye whichcontains a precursor of the reactive radical and subsequently convertingthis precursor into the end stage, for example by esterification or anaddition reaction. For example, it is possible to prepare a dye of theformula (4) in which X is a HO--CH₂ CH₂ -- radical and to react theintermediate with sulfuric acid before or after the acylation, so thatthe hydroxyl group is converted into the sulfato group; or to use ananalogous dye in which X is the vinyl group, H₂ C═CH--, and to addthiosulfuric acid onto the intermediate, forming a HO₃ SS--CH₂ CH₂ --radical. The sulfation of the hydroxyl group in a dye of the formula (4)or a suitable precursor is effected for example by reaction at 0° C. tomoderately elevated temperatures with concentrated sulfuric acid. Thesulfation can also be effected by reacting the hydroxy compound with 2equivalents of chlorosulfonic acid per hydroxyl group at 10° to 80° C.in a polar organic solvent, for example N-methylpyrrolidone. Thesulfation is preferably effected by adding the compound in question attemperatures between 5° and 15° C. to sulfuric acid monohydrate. Theintroduction into a compound of the formula (1) or an intermediate, of aradical detachable under alkaline conditions, for X other than thesulfato group, for example a thiosulfato group, is effected in a mannerknown per se.

Moreover, elimination reactions can be carried out subsequently to thesynthesis. For example, the reactive dyes of the formula (1) whichcontain sulfatoethylsulfonyl radicals can be treated withacid-eliminating agents, such as sodium hydroxide, and thesulfatoethylsulfonyl radicals turn into vinylsulfonyl radicals.

In many cases the method of preparation described above, namely via anintermediate of the reactive radical, has just a single product and goesto completion.

If groups capable of metal complex formation are present in the reactivedyes prepared, the reactive dyes can also be subsequently metallised.

As the individual steps of the process given above can be carried out indifferent orders, there are various possible process variants. Ingeneral the reaction is carried out in successive steps, the order ofthe elementary reactions between the individual reactants advantageouslybeing arranged in accordance with the particular conditions. Ashydrolysis of the 2,4-difluoro-5-chloropyrimidyl radical can occur undercertain conditions, an intermediate which contains acetylamino groupshas to be hydrolysed (to split off the acetyl groups) before thecondensation with 2,4,6-trifluoro-5-chloropyrimidine. Which part of theoverall reaction is advantageously carried out first varies from case tocase and is arranged especially according to the solubility of the aminocompounds involved and the basicity of the amino groups to be acylated.The acylation of the dyes of the formula (4) or the dye precursors with2,4,6-trifluoro-5-chloropyrimidine is effected by methods known per se,preferably in aqueous solutions or suspensions and in the presence ofalkaline acid-binding agents, for example aqueous alkali metalhydroxides, carbonates or bicarbonates.

The most important process variants are reflected in the illustrativeembodiments.

There now follow specific examples of possible starting materials whichcan be used for preparing the reactive dyes of the formula (1).

The dyes of the formula (4) can be in particular dyes of the followingstructural types: ##STR10##

If, in preparing the reactive dyes of the formula (1), the startingmaterials are not finished amino dyes, for example are not thosedescribed above, but are dye precursors, i.e. diazo and couplingcomponents, one of the two components has to have at least oneacylatable amino group and the other at least one X--SO₂ -- group.Possible diazo components are in the main suitable compounds of theaminobenzene and aminonaphthalene series, for example those contained inthe azo dyes of the formulae given above, such as 1,3-diaminobenzene,1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene,1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene,1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene,1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,4-diamino-2-ethoxybenzene, 1,4-diamino-2-chlorobenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene,1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene,1,4-diamino-2,5-diethoxybenzene 2,6-diaminonaphthalene,1,3-diamino-2,4,6-trimethylbenzene,1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene,4,4'-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4' -diaminobiphenyl(benzidine), 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine,3,3'-dicarboxymethoxybenzidine, 2,2'-dimethylbenzidine,4,2'-diaminodiphenyl (diphenyline),2,6-diaminonaphthalene-4,8-disulfonic acid,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2, 5-disulfonicacid, 1,4-diaminobenzene-2,6-disulfonic acid,1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonicacid, 1,4-diamino-2-chlorobenzene-5-sulfonic acid,1,4-diamino-2-methylbenzene-5-sulfonic acid,1,5-diamino-6-methylbenzene-3-sulfonic acid,1,3-diamino-6-methylbenzene-4-sulfonic acid, 3-(3'- or4"-aminobenzoylamino)-1-aminobenzene-6-sulfonic acid,1-(4'-aminobenzoylamino)-4-aminobenzene-2,5-disulfonic acid,1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylicacid, 1,2-diaminobenzene-4-carboxylic acid,1,3-diaminobenzene-5-carboxylic acid, 1,4-diamino-2-methylbenzene,4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylurea-2,2'-disulfonicacid, 4,4'-diaminodiphenyloxyethan-2,2'-disulfonic acid,4,4'-diaminostilbene-2,2'-disulfonic acid,4,4'-diaminodiphenylethane-2,2'-disulfonic acid,2-amino-5-aminomethylnaphthalene-1-sulfonic acid,2-amino-5-aminomethylnaphthalene-1,7-disulfonic acid,1-amino-4-methoxy-5-aminomethylbenzene-6-sulfonic acid and1,3,5-triaminobenzene.

Examples of aromatic amines which can serve as diazo components inpreparing the monoazo or disazo dyes and which contain one or two bondedgroups of the formula X--SO₂ -are:

1-Amino-4-β-sulfatoethylsulfonylbenzene,1-amino-4-β-thiosulfatoethylsulfonylbenzene,1-amino-4-vinylsulfonylbenzene, 1-amino-4-β-chloroethylsulfonylbenzene,1-amino-3-β-sulfatoethylsulfonylbenzene, 1-amino-3-vinylsulfonylbenzene,1-amino-2-methoxy-5-β-sulfatoethylsulfonylbenzene,1-amino-2-methoxy-5-β-thiosulfatoethylsulfonylbenzene,1-amino-2-methoxy-5-vinylsulfonylbenzene,1-amino-4-methoxy-3-β-sulfatoethylsulfonylbenzene,1-amino-4-methoxy-3-β-vinylsulfonylbenzene,1-amino-2,5-dimethoxy-4β-sulfatoethylsulfonylbenzene,1-amino-2,5-dimethoxy-4-vinylsulfonylbenzene,1-amino-2-methoxy-4-β-sulfatoethylsulfonyl-5-methylbenzene,1-amino-2-methoxy-4-vinylsulfonyl-5-methylbenzene,1-amino-3-β-sulfatoethylsulfonyl-6-carboxybenzene,1-amino-3-vinylsulfonyl-6-carboxybenzene,1-amino-4-β-sulfatoethylsulfonylbenzene-2-sulfonic acid,1-amino-4-vinylsulfonylbenzene-2-sulfonic acid,1-amino-5-vinylsulfonylbenzene-2,4-disulfonic acid,1-amino-2-hydroxy-5-βsulfatoethylsufonylbenzene,1-amino-2-hydroxy-4-β-sulfatoethylsulfonylbenzene,1-amino-2-hydroxy-4-β-sulfatoethylsulfonylbenzene,1-amino-2-hydroxy-5-β-sulfatoethylsulfonyl-benzene-3-sulfonic acid,1-amino-2-bromo-4-β-sulfatoethylsulfonylbenzene,1-amino-2,6-dichloro-4-β-sulfatoethylsulfonylbenzene,1-amino-2,4-di-(β-sulfatoethylsulfonyl)-benzene,1-amino-2,4-di-(β-sulfatoethylsulfonyl)-5-chlorobenzene,1-amino-2,4-di-(β-thiosulfatoethylsulfonyl)-5-chlorobenzene,1-amino-2,4-di-(vinylsulfonyl)-benzene, 1-amino-2,4-di-(vinylsulfonyl)-5-chlorobenzene,1-amino-2,4-di-β-acetoxyethylsulfonyl)-benzene,1-amino-2,4-di-(β-acetoxy-ethylsulfonyl)-5-chlorobenzene,2-amino-8-βsulfatoethylsulfonylnaphthalene,2-amino-6-β-sulfatoethylsulfonylnaphthalene,2-amino-6-β-sulfatoethylsulfonylnaphthalene-1-sulfonic acid,2-amino-8-β-sulfatoethylsulfonylnaphthalene-6sulfonic acid and2-amino-6,8-di-(β-sulfatoethylsulfonyl)-naphthalene.

A mention should also go to the corresponding β-hydroxy compounds whichcan be used as precursors, examples being1-amino-4-β-hydroxyethylsulfonylbenzene,1-amino-3-β-hydroxyethylsulfonylbenzene,1-amino-2,4-di-(β-hydroxyethylsulfonyl)-benzene and1-amino-2,4-di-(β-hydroxyethyl-sulfonyl)-5-chlorobenzene.

If the diazo component to be used is not a diamine but is anaminoacetylamino compound from which the acetyl group is subsequently tobe reeliminated by hydrolysis, as mentioned above in the description ofthe process, the monoacetyl compounds of the abovementioned diazocomponents are possible, examples being1-acetylamino-3-aminobenzene-4-sulfonic acid and1-acetylamino-4-aminobenzene-3-sulfonic acid.

The coupling components are chiefly suitable compounds of theaminobenzene and naphthalene series, for example anilines,N-monosubstituted anilines, m-phenylenediamine derivatives,aminonaphthalenes, naphthols, aminonaphthalenesulfonic acid,naphtholsulfonic acids or aminonaphtholsulfonic acids and alsopyrazolones, aminopyrazoles, aminopyridines, hydroxypyridines/pyridones,aminopyrimidines, hydroxypyrimidines, indoles, barbituric acidderivatives or acetoacetarylides. Examples are 1-amino-3-methylbenzene,1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene,3-aminophenylurea, 1-amino-3-acetylaminobenzene,1-amino-3-hydroxyacetylaminobenzene, 1,3-diaminobenzene-4-sulfonic acid,1-aminonaphthalene-6- or -8-sulfonic acid,1-amino-2-methoxynaphthalene-6-sulfonic acid,2-aminonaphthalene-5,7-disulfonic acid,1-amino-8-hydroxynaphthalene-6-sulfonic acid,1-amino-8-hydroxynaphthalene-2,4-disulfonic acid,2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid,1-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl-or2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid,2-amino-5-hydroxynaphthalene-1,7-disulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl- or2-ethyl-amino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-8-hydroxynaphthalene-3,6-disulfonic acid,1-amino-5-hydroxy-naphthalene-7-sulfonic acid,1-amino-8-hydroxynaphthalene3,6- or -4,6-disulfonic acid,1-(4'-aminobenzoylamino)-8-hydroxynaphthalene-3,6- or -4,6-disulfonicacid, 2-(4'-amino-3'-sulfophenylamino)-5-hydroxynaphthalene-7-sulfonicacid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid,2,4,6-triamino-3-cyanopyridine,1-β-aminoethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one,1-γ-aminopropyl-3-sulfomethyl-4-methyl-6-hydroxypyrid-2-one,1,3-diaminobenzene, 1-amino-3-(N,N-di-β-hydroxyethylamino)-benzene,1-amino-3-(N,N-di-β-sulfatoethylamino)-benzene, 1-amino-3-(N,N-di-β-hydroxyethylamino)-4-methoxybenzene,1-amino-3-(N,N-di-β-sulfatoethylamino)-4-methoxybenzene,1-amino-3-sulfobenzylaminobenzene,1-amino-3-sulfo-benzylamino-4-chlorobenzene,1-amino-3-(N,N-di-sulfo-benzylamino)-benzene,1-(3'-aminophenyl)-3-methyl-5-pyrazolone as well as1-(aminophenyl)-3-carboxy-5-pyrazolones which can be substituted in thephenyl nucleus by chlorine, methyl, methoxy, nitro or sulfo, such as1-(2'-sulfo-4'-aminophenyl)-3-carboxypyrazol-5-one.

If one of the two components contains both reactive groups at the sametime or these can be introduced into the component in question, as inthe case of the coupling components of the formulae ##STR11## the othercomponent, in this case the diazo component, can also be non-reactive.Examples are aminobenzene, 1-amino-2-, -3- or -4-methylbenzene,1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or-4-chlorobenzene, 1-amino-2,5-dichlorobenzene,1-amino-2,5-dimethylbenzene, 1-amino-3-methyl-6-methoxybenzene,1-amino-2-methoxy-4-nitrobenzene, 1-aminobiphenyl, 2-aminodiphenylether, 1-aminobenzene-2-, -3- or -4-sulfonamide, 1-aminobenzene-2-, -3-or -4-carboxylic acid, dehydrothio-p-toluidine-sulfonic acid,1-amino-3-trifluoromethylbenzene-6-sulfonic acid, 1-aminobenzene-2-, -3-or -4-sulfonic acid, 1-aminobenzene-2,4- and -2,5-disulfonic acid,1-amino-4-methylbenzene-2-sulfonic acid,1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or-4-sulfonic acid, 1-amino-2-carboxybenzene-4-sulfonic acid,1-amino-4-carboxybenzene-2-sulfonic acid, 1-amino-4- or-5-chlorobenzene-2-sulfonic acid, 1-amino-6-chlorobenzene-3- or-4-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid,1-amino-2,5-dichlorobenzene-6-sulfonic acid,1-amino-2,5-dichlorobenzene-4-sulfonic acid,1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid,1-amino-5-methyl-4-chlorobenzene-2-sulfonic acid, 1-amino-4- or-5-methoxybenzene-2-sulfonic acid, 1-amino-6-methoxybenzene-3- or-4-sulfonic acid, 1-amino-6-ethoxybenzene-3- or -4-sulfonic acid,1-amino-2,4-dimethoxybenzene-6-sulfonic acid,1-amino-2,5-dimethoxybenzene-6sulfonic acid,1-amino-2,5-dimethoxybenzene-4-sulfonic acid,1-amino-3-acetylaminobenzene-6-sulfonic acid,1-amino-4-acetylaminobenzene-2-sulfonic acid,1-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid,2-amino-1-methylbenzene-3,5-disulfonic acid,1-amino-4-methoxybenzene-2,5-disulfonic acid, 1-amino-3- or-4-nitrobenzene-6-sulfonic acid, 1-aminonaphthalene, 2-aminonaphthalene,1-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid,2-aminonaphthalene-1-, -3-, -4-, -5-, -6-, -7- or -8-sulfonic acid,2-aminonaphthalene-3,6- or -5,7-disulfonic acid, 1-aminonaphthalene-3,6-or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-,-4,8- or -6,8-disulfonic acid, 1-aminonaphthalene-2,5,7-trisulfonicacid, 2-aminoacid, naphthalene-1,5,7-, -3,6,8- or -4,6,8-trisulfonicacid, 1-hydroxy-2-aminobenzene-4-sulfonic acid,1-hydroxy-2-aminobenzene-5-sulfonic acid,1-hydroxy-2-aminobenzene-5-sulfonic acid,1-hydroxy-2-aminobenzene-4,6-disulfonic acid,1-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid,1-hydroxy-2-amino-o-acetylaminobenzene-4-sulfonic acid,1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid,1-hydroxy-2-amino-4-methylsulfonylbenzene,1-amino-2-hydroxy-6-nitronaphthalene-6-sulfonic acid,2-amino-1-hydroxynaphthalene-4,8-disulfonic acid,4-aminoazobenzene-3,4'-disulfonic acid,3-methoxy-4-amino-6-methylazobenzene-2',4'-disulfonic acid and3-methoxy-4-amino-6-methylazobenzene-2',5'-disulfonic acid.

The diazotisation of the intermediates containing a diazotisable aminogroup is generally effected at low temperatures by the action of nitrousacid in aqueous mineral acid solutions, coupling taking place at weaklyacid, neutral or weakly alkaline pH.

The condensation of 2,4,6-trifluoro-5-chloropyrimidine with the diazocomponents or the coupling components or with acylatable monoazo ordisazo intermediates or with the amino-containing dyes of the formula(4) or their precursors preferably takes place at low temperatures andweakly acid, neutral or weakly alkaline pH in aqueous solutions orsuspensions. The hydrogen fluoride set free during the condensation isadvantageously continuously neutralised by adding aqueous alkali metalhydroxides, carbonates or bicarbonates.

The reactive dyes of the formula (1) are fibre-reactive. Fibre-reactivecompounds are to be understood as meaning those capable of reacting withthe hydroxyl groups of cellulose or with amino groups of natural orsynthetic polyamides to form covalent chemical bonds.

The reactive dyes of the formula (1) are suitable for dyeing andprinting a very wide variety of different materials, such as silk,leather, wool, nylon fibres and polyurethanes, and in particularcellulose-containing fibre materials of any kind. Examples of such fibrematerials are the natural cellulose fibre, such as cotton, linen andhemp, as well as pulp and regenerated cellulose. The reactive dyes ofthe formula (1) are also suitable for dyeing or printinghydroxyl-containing fibres contained in blend fabrics, for exampleblends of cotton with polyester fibres or nylon fibres.

The dyes according to the invention can be applied to the fibre materialand fixed on the fibre in various ways, in particular in the form ofaqueous dye solutions and print pastes. They are suitable not only forthe exhaust method of dyeing but also for dyeing by the pad-dyeingmethod whereby the cloth is impregnated with aqueous dye solutions whichcan, if desired, also contain salt, and the dyes are fixed, if desiredunder heat, after a treatment with alkali or in the presence of alkali.They are particularly suitable for the so-called cold pad-batch methodwhereby the dye is applied on a pad-mangle together with the alkali.After the fixing the dyeings or prints are thoroughly rinsed with coldand hot water which can, if desired, also contain an agent acting like adispersant and promoting the diffusion of the unfixed portions.

The reactive dyes of the formula (1) are distinguished by highreactivity and good fixing properties. They can therefore be used inexhaust dyeing at low dye temperatures and require only short steamingtimes in the padsteam process. The degrees of fixation are high, and theunfixed portions are readily washed off, the difference between thedegree of exhaustion and the degree of fixation being remarkably small,i.e. the hydrolysis loss being very low. The reactive dyes of theformula (1) are also suitable for printing, especially on cotton, butalso for printing nitrogen-containing fibres, for example wool, silk orwool-containing blend fabrics.

The dyeings and prints prepared with the dyes according to the inventionare distinguished by bright shades. In particular the dyeings and printson cellulose fibre materials are of high tinctorial strength and have ahigh fibre-dye bond stability not only in the acid but also in thealkaline range, and also good lightfastness and very good wetfastnessproperties, such as wash, water, sea water, cross-dyeing andperspiration fastness properties, as well as a good fastness topleating, hot-press fastness and rub fastness.

The following examples serve to illustrate the invention. Thetemperatures are given in degrees centigrade. The parts and percentagesare by weight, unless otherwise stated. Parts by weight relate to partsby volume as the kilogramme relates to the liter.

The preparation of the monoazo or disazo intermediates has not beendescribed in all cases in the following illustrative embodiments, but itis anyhow readily apparent from the general description.

EXAMPLE 1

30.3 parts of 2-naphthylamine-4,8-disulfonic acid are suspended in 400parts by volume of ice-water. 25 parts by weight of concentratedhydrochloric acid are added, and the mixture is diazotised with 20 partsby volume of 5N sodium nitrite. The diazotisation mixture is thenstirred at 0° to 5° C. for 1 hour, and the excess nitrous acid is thendestroyed with a little sulfamic acid. 33.1 parts of1-naphthylamine-6β-sulfatoethyl sulfone are then added, and the mixtureis gradually brought to pH 4.5 by means of sodium acetate. It is thenstirred at this pH and 10° to 15° C. for a further 2 hours until freediazonium compound is no longer detectable. The mixture is then cooledback again to 0° to 5° C., 35 parts of concentrated hydrochloric acidare added, followed by 22 parts by volume of 5N sodium nitrite solution.The mixture is stirred at 0° to 5° C. for 1 hour, and a little sulfamicacid is then added.

To the solution are then added 22.5 parts of 1-naphthylamine-8-sulfonicacid, and the mixture is brought to pH 4-5 with about 15 parts of sodiumcarbonate and is maintained at that pH for 2 hours of stirring. The dyesolution is then brought to pH 5.5-6.0 and is cooled down to 10° C. Atthis temperature and this pH 15 parts of2,4,6-trifluoro-5-chloropyrimidine are added dropwise, and the mixtureis then stirred for 1 hour during which pH 5.5-6.0 is maintained. Thedyestuff is precipitated out of solution with potassium chloride andsodium chloride.

Drying at 40° to 50° C. and grinding produce a black dye powder whichcontains the alkali metal salt of the compound of the formula ##STR12##This compound has very good dye properties and dyes cotton and wool bythe dyeing and printing methods customary for reactive dyes in brownshades having very good wetfastness properties.

EXAMPLE 2

18.8 parts of 1,3-diaminobenzene-4-sulfonic acid are added to 200 partsof water, and the mixture is neutralised with sodium carbonate. 16.9parts of 2,4,6-trifluoro5-chloropyrimidine are added dropwise at roomtemperature in the course of an hour. A constant pH 6.5 is maintainedwith 2N NaOH, and the temperature must not exceed 30° C. After thecondensation has ended the fine suspension is filtered and the filtercake is washed with 5% sodium chloride solution. The filter cake isacidified with 35 parts by volume of 31% strength aqueous hydrochloricacid, 500 parts of ice are added to it, and it is diazotised by slowlyadding 20 parts by volume of aqueous 5N sodium nitrite solution. Ascustomary, the excess nitrous acid is then destroyed with a littlesulfamic acid. The mixture is then added to a solution of 31.9 parts of1-amino-8-naphthol-3,6-disulfonic acid in 500 parts of water which hasbeen adjusted to pH 4 with hydrochloric acid, and the coupling reactioncommences. The coupling is maintained at pH 2-3.0 with sodium carbonate.After the first coupling reaction has ended the monoazo compound formedis reacted in the second coupling reaction with a diazonium saltsolution. This diazonium salt solution is prepared as follows:

a mixture of a neutral solution of 28.1 parts of aniline 4β-sulfatoethylsulfone in 150 parts of water and 20.3 parts by volume of aqueous 5Nsodium nitrite solution is added at 0 ° to 5° C. with stirring to amixture of 26 parts by volume of 31% strength aqueous hydrochloric acidand 150 parts of ice. The resulting suspension is then stirred for anhour, and excess nitrous acid is destroyed with sulfamic acid. Thediazonium salt suspension is then brought to pH 5.5-6.5 with 17.8 partsof sodium bicarbonate and is coupled at pH 5.5-6.5 as mentioned abovewith the solution of the monoazo compound. The disazo compound formed issalted out with sodium chloride, is filtered off with suction and isdried.

The result is an alkali metal salt of the compound of the formula##STR13## in the form of a black electrolyte-containing powder. Thiscompound has very good dye properties and produces on cellulose fibrematerials by the industrially customary application and fixing methodsnavy dyeings and prints having very good end-use and manufacturingfastness properties. Wool is likewise dyed navy from a weakly acid bath,the wetfast properties of these navy dyeings being excellent after anaftertreatment with ammonia.

The disazo compounds according to the invention and having the generalformula ##STR14## which are characterised in the tabled examples belowby means of the indicated radicals are prepared analogously to theprevious example by first of all, correspondingly, preparing a diazocomponent which is the reaction product of2,4,6-trifluoro-5-chloropyrimidine and a diaminobenzene compound, thendiazotising this diazo component and coupling it onto1-amino-8-naphthol-3,6- or -4,6-disulfonic acid, and thereupon reactingthe monoazo compound formed with an aniline derivative having aβ-sulfatoethylsulfonyl group as the second diazo component. Thesecomponents of the reaction are apparent from the tabled examples inconjunction with the above general formula. The disazo compoundsaccording to the invention which are described in these Examples 3 to 12likewise have very good fibre-reactive dye properties and, for exampleon cotton materials, produce fast dyeings in the hues given in theexamples.

                                      TABLE                                       __________________________________________________________________________    Ex-                         Position of                                                                         Hue on                                      ample                                                                             D.sub.2       D.sub.1   HO.sub.3 S                                                                          cotton                                      __________________________________________________________________________         ##STR15##                                                                                   ##STR16##                                                                              3     greenish navy                               4                                                                                  ##STR17##    "         3     navy                                        5                                                                                  ##STR18##    "         3     navy                                        6   "             "         4     navy                                        7                                                                                  ##STR19##                                                                                   ##STR20##                                                                              3     greenish navy                               8                                                                                  ##STR21##                                                                                   ##STR22##                                                                              3     navy                                        9                                                                                  ##STR23##                                                                                   ##STR24##                                                                              3     greenish black                              10                                                                                 ##STR25##                                                                                   ##STR26##                                                                              3     greenish black                              11                                                                                 ##STR27##                                                                                   ##STR28##                                                                              3     black                                       12                                                                                 ##STR29##                                                                                   ##STR30##                                                                              3     black                                       __________________________________________________________________________

Dyeing method I

2 parts of the dye obtained in Example 1 are dissolved in 400 parts ofwater; to this solution are added 1,500 parts of a solution whichcontains per liter 53 g of sodium chloride. 100 parts of a cotton fabricare introduced at 40° C. into this dyebath. After 45 minutes 100 partsof a solution which contains per litre 16 g of sodium hydroxide and 20 gof calcined sodium carbonate are added. The temperature of the dyebathis held at 40° C. for a further 45 minutes. The dyed fabric is thenrinsed, is soaped off at the boil with a nonionic detergent for aquarter of an hour, is rinsed once more and is dried.

Dyeing method II

2 parts of the reactive dye obtained in Example 1 are dissolved in 400parts of water; to this solution are added 1,500 parts of a solutionwhich contains per liter 53 g of sodium chloride. 100 parts of a cottonfabric are introduced at 35° C. into this dyebath. After 20 minutes 100parts of a solution which contains per litre 16 g of sodium hydroxideand 20 g of calcined sodium carbonate are added. The temperature of thedyebath is held at 35° C. for a further 15 minutes. The temperature isthen raised to 60° C. in the course of 20 minutes. The temperature isheld at 60° C. for a further 35 minutes. The fabric is then rinsed, issoaped off at the boil with a nonionic detergent for a quarter of anhour, is rinsed once more and is dried.

Dyeing method III

8 parts of the reactive dye obtained in Example 1 are dissolved in 400parts of water; to this solution are added 1,400 parts of a solutionwhich contains per litere 100 g of sodium sulfate. 100 parts of a cottonfabric are introduced at 25° C. into this dyebath. After 10 minutes 200parts of a solution which contains per liter 150 g of trisodiumphosphate are added. The temperature of the dyebath is then raised to60° C. in the course of 10 minutes. The temperature is held at 60° C.for a further 90 minutes. The fabric is then rinsed, is soaped off atthe boil with a nonionic detergent for a quarter of an hour, is rinsedonce more and is dried.

Dyeing method IV

4 parts of the reactive dye obtained in Example 1 are dissolved in 50parts of water; to this solution are added 50 parts of a solution whichcontains per liter 5 g of sodium hydroxide and 20 g of calcined sodiumcarbonate. The resulting solution is applied to a cotton fabric on apad-mangle in such a way that its weight increases by 70%, and thefabric is then wound onto a beam. In this state the cotton fabric isleft to stand at room temperature for 3 hours. The dyed fabric is thenrinsed, is soaped off at the boil with a nonionic detergent for aquarter of an hour, is rinsed once more and is dried.

Dyeing method V

6 parts of the reactive dye obtained in Example 1 are dissolved in 50parts of water; to this solution are added 50 parts of a solution whichcontains per liter 16 g of sodium hydroxide and 0.04 liter of sodiumsilicate. The resulting solution is applied to a cotton fabric on apad-mangle in such a way that its weight increases by 70%, and thefabric is then wound onto a beam. In this state the cotton fabric isleft at room temperature for 10 hours. The dyed fabric is then rinsed,is soaped off at the boil with a nonionic detergent for a quarter of anhour, is rinsed once more and is dried.

Dyeing method VI

2 parts of the reactive dye obtained in Example 1 are dissolved in 100parts of water in the presence of 0.5 part of sodiumm-nitrobenzenesulfonate. The resulting solution is used to impregnate acotton fabric in such a way that its weight increases by 75%, and thefabric is then dried. The fabric is then impregnated with a warmsolution at 20° C. which contains per litre 4 g of sodium hydroxide and300 g of sodium chloride, and is squeezed to a 75% weight increase andthe dyeing is steamed at 100 ° to 102° C. for 30 seconds, is rinsed, issoaped off at the boil with a 0.3% strength solution of a nonionicdetergent for a quarter of an hour, is rinsed and is dried.

Printing method I

3 parts of the reactive dye obtained in Example 1 are sprinkled withhigh-speed stirring into 100 parts of stock thickening containing 50parts of 5% strength sodium alginate thickening, 27.8 parts of water, 20parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts ofsodium hydrogencarbonate. The print paste thus obtained is used to printa cotton fabric, which is then dried, and the resulting printed fabricis steamed at 102° C. in saturated steam for 2 minutes. The printedfabric is then rinsed, if desired soaped off at the boil and rinsed oncemore, and is then dried.

Printing method II

5 parts of the reactive dye obtained in Example 1 are sprinkled withhigh-speed stirring into 100 parts of a stock thickening containing 50parts of 5% strength sodium alginate thickening, 36.5 parts of water, 10parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 2.5 parts ofsodium hydrogencarbonate. The print paste thus obtained, whose stabilitymeets industrial requirements, is used to print a cotton fabric, whichis then dried, and the resulting printed fabric is steamed at 102° C. insaturated steam for 8 minutes. The printed fabric is then rinsed, ifdesired soaped off at the boil and rinsed once more, and is then dried.

I claim:
 1. A reactive dye of the formula ##STR31## in which X is vinyl, β-sulfatoethyl, βthiosulfatoethyl, β-chloroethyl or β-acetoxyethyl, and the benzene and naphthalene rings A, B and B', independently of one another, are unsubstituted or substituted by a member selected from the group consisting of alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, acylamino having 1 to 8 carbon atoms, amino, alkylamino having 1 to 4 carbon atoms, phenylamino, N,N-di-β-hydroxyethylamino, N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, alkylsulfonyl having 1 to 4 carbon atoms, trifluoromethyl, nitro, cyano, halogen, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms, N-(β-hydroxyethyl)-sulfamoyl, N,N,-di-(β-hydroxyethyl)-sulfamoyl, N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfo.
 2. A reactive dye according to claim 1 in which X is vinyl or β-sulfatoethyl. 